Simple & Fractional Distillation

Experiment Simple & Fractional Distillation

Evaluation of the relative effectiveness of Simple & Fractional
Distillation to separate mixtures of organic compounds based
on differences in Boiling Point
Determination of Mole % from Distillate Volume Data, Gas
Chromatography, and Refractive Index
Text References
Slayden p. 39-41, 43-46, 47
Pavia - Tech 14.1 - 14.3; p. 719 729 (Simple Distillation)
Pavia - Tech 15.1 - 15.6; p. 729 740 (Fractional distillation)
Pavia - Tech 22.1 22.12; p. 817 836 (Gas Chromatography)
Pavia - Tech 24; p. 845 850 (Refractive Index)

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1
Simple & Fractional Distillation
Overview
A mixture of Ethyl Acetate and Butyl Acetate
(unknown mole %) will be subjected to both a Simple
Distillation and a Fractional Distillation (using a
Vigreux Fractionation Column)
Each distillation will result in three (3) vials (fractions)
of distillate representing 3 temperature ranges
(0-95
o
C; 95 -105
o
C; and 105-130
o
C)
Volume recovery of total distillate as well as volume
recovery of the distillate fractions will be computed
Fractions 1 & 2 will be combined mathematically and
assumed to be Ethyl Acetate
Fraction 3 will be assumed to be Butyl Acetate

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Simple & Fractional Distillation
Overview (cont)
From the volumes and respective densities, the mass, moles,
mole fraction, and mole % will be computed.
Gas Chromatograms of the 6 distillate vials (3 from Simple
Distillation & 3 from Fractional Distillation) plus the original
unfractionated mixture will be obtained
Mole % of the components in each fraction will be
computed based on the relationship between peak area
(readjusted for non-linear thermal response) and mole
content
If directed by instructor, Mole % values will also be determined
from a standard Regression Curve relating Refractive Index of
known mixtures of Ethyl & Butyl Acetate to the measured
Refractive Index values of the distillate fractions
Distillation results and mole % values will be used to evaluate
the relative effectiveness of component separation by Simple
Distillation vs Fractional Distillation
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Simple & Fractional Distillation
Vapor Pressure / Boiling Point
According to Kinetic Theory, the molecules in a liquid are in
a constant state of thermal motion and some of these
molecules are moving fast enough to escape from the
liquid forming a vapor above the liquid. This vapor exerts a
pressure on the surface of the liquid, i.e., Vapor Pressure
Vapor Pressure The pressure of the vapor coexisting with
a confined liquid or solid, i.e., the pressure in an evacuated
container containing a liquid at constant temperature after
the liquid and escaping molecules near the surface of the
liquid the vapor - reach equilibrium
The Vapor Pressure of a liquid increases, generally
exponentially, with temperature
Boiling Point As a liquid is heated, the vapor pressure of
the liquid increases to the point at which it just equals the
applied pressure - usually atmospheric pressure. The liquid
now begins to bubble (boil)
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Simple & Fractional Distillation
Vapor Pressure / Boiling Point
Boiling Point
The normal boiling point (also called the atmospheric
boiling point or the atmospheric pressure boiling point)
of a liquid is the temperature at which the vapor
pressure of the liquid is equal to the atmospheric
pressure.
At that temperature, the vapor pressure of the liquid
becomes sufficient to overcome atmospheric pressure
and allow bubbles of vapor to form inside the bulk of
the liquid
The standard boiling point is now (as of 1982) defined
by IUPAC as the temperature at which boiling occurs
under a pressure of 1 bar
1 bar = 10
5
Pascals = 0.98692 atmospheres (atm)
= 14.5038 psi (pounds per square inch)
= 29.53 in Hg (inches of mercury) = 750.06 mm
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Simple & Fractional Distillation
Distillation / Boiling Point Measurement
Note: The temperature range you obtain for your boiling
point may be inaccurate for three (3) reasons
1. The atmospheric pressure in the lab may not be:
1 bar (0.98692 atm)
2. The thermometers used in the lab may not
reflect the actual temperature
3. The thermal inefficiency of the glassware used for
the boiling point determination may result in a
lower than expected measured value by as much
as 2 5
o
C
You should take this potential temperature differential
into account when you compare your measured results
with the list of possible unknowns in lab manual tables
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Simple & Fractional Distillation
Vapor Pressure / Boiling Point (Cont)
Different liquid compounds or mixtures of liquids have
different vapor pressures at a given temperature
Liquids with high vapor pressures (Volatile compounds)
require relatively little energy (heat) to increase the
vapor pressure to match the applied (atmospheric)
pressure, and thus, boil, i.e. they have low boiling points
Liquids with low vapor pressures require considerably
more energy to increase the vapor pressure to the point
where it matches the applied pressure, thus, they have
relatively high boiling points
The individual compounds in a mixture each exert its
own pressure partial pressure
The sum of the partial pressures equals to the total
vapor pressure of the solution
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Simple & Fractional Distillation
Raoults Law
In a solution of two miscible liquids (A & B) the partial
pressure of component A (P
A
) in the solution equals
the partial pressure of pure A (P
A
o
) times its mole
fraction (N
A
)
Partial Pressure of A in solution = P
A
= (P
A
o
) x (N
A
)
Partial Pressure of B in solution = P
B
= (P
B
o
) x (N
B
)
When the total pressure (sum of the partial pressures) is
equal to or greater than the applied pressure, normally
Atmospheric Pressure (760 mm Hg), the solution boils
P
total
= P
A
+ P
B
=

P
A
o
N
A
+ P
B
o
N
B
If the sum of the two partial pressures of the two
compounds in a mixture is less than the applied pressure,
the mixture will not boil. The solution must be heated until
the combined vapor pressure equals the applied pressure
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Simple & Fractional Distillation
Raoults Law (Cont)
Example
Consider a solution at 100
o
C where N
A
= 0.5 and N
B
= 0.5
What is the Partial Pressure of A in the solution if the Vapor
Pressure of Pure A at 100
o
C is 1020 mm Hg?
Ans: P
A
= P
o
A
N
A
= (1020) * (0.5) = 510 mm Hg
What is the Partial Pressure of B in the solution if the Vapor
Pressure of Pure B at 100
o
C is 500 mm Hg?
Ans: P
B
= P
o
B
N
B
= (500) * (0.5) = 250 mm Hg
Would the solution boil at atmospheric pressure (760 mm Hg)?
Ans: Yes P
total
= P
A
+ P
B
= (510 + 250) = 760 mm Hg
What is the composition of the Vapor at the Boiling Point?
Ans: The mole fraction of each would be:
N
A
(vapor) = P
A
/ P
total
= 510/760 = 0.67
N
B
(Vapor) = P
B
/ P
total
= 250/760 = 0.33
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Simple & Fractional Distillation
Distillation
Process of vaporizing a liquid, condensing the vapor,
and collecting the condensate in another container
Uses of Distillation
Separating liquids with different boiling points
Purifying a liquid.
Distillation Methods
Simple
Vacuum (at reduced pressure)
Fractional
Steam
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Simple & Fractional Distillation
Distillation (Cont)
Pure Substance
Temperature remains constant during distillation
process so long as both vapor and liquid are
present
Miscible Liquid Mixture
Temperature increases throughout process because
composition of vapor changes continuously
Composition of vapor in equilibrium with the heated
liquid is different from the composition of the liquid
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Simple & Fractional Distillation
Simple Distillation
Single Vaporization / Condensation cycle of a mixture
that produces a distillate that is always impure at any
temperature range between the range of boiling points
of the components
Therefore, it is impossible to completely separate the
components in a mixture with Simple Distillation
Relatively pure substances can be obtained from a
mixture with Simple Distillation if the boiling points of
the components differ by a large amount (>100
o
C)
If a small increment of the initial distillate is separated
and redistilled and this process is repeated many times,
effectively producing multiple sequential Vaporization/
Condensation Cycles, an increasingly pure solution can
be attained. This would be a very tedious process
involving a large number of distillations
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Simple & Fractional Distillation
Fractional Distillation
Accomplishes the same thing as Multiple Simple
Sequential Vaporization / Condensation Cycles, by
inserting a Fractionating Column (a Vigreux Column)
between the Distillation Flask and the Distillation Head
The Fractionating Column, of which there are many
types containing a variety of packing materials, subjects
the mixture to many Vaporization/Condensation Cycles
as the material moves up the column toward the
Distillation Head, which is attached to the Condenser
With each cycle within the column, the composition of
the vapor is progressively enriched in the lower boiling
liquid
This process continues until most of the lower boiling
compound is removed from the original mixture and
condensed in the receiving flask
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Simple & Fractional Distillation
Fractional Distillation (Cont)
When the lower boiling liquid is effectively removed
from the original mixture, the temperature rises and a
second fraction containing some of both compounds is
produced
As the temperature approaches the boiling point of
the higher boiling point compound, the distillate
condensing into the third receiving flask is increasingly
pure in the higher boiling point compound
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Simple & Fractional Distillation
Fractional Distillation (Cont)
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15
As the distillation proceeds, the
composition of the liquid and the vapor
are continuously changing
The Horizontal and Vertical Lines
represent the processes that occur during
a fractional distillation.
Each Horizontal Line (L
3
V
3
, L
2
,V
2
), etc.,
represents both the vaporization step of a
given vaporization/condensation step and
the composition of the vapor in
equilibrium with the liquid at a given
temperature.
Examples:
At 53
o
C with a liquid composition of 80% A
and 20% B (L
4
V
4
on the diagram), the
vapor would have 95% A and 5% B when
equilibrium has been established between
the liquid and the vapor.
At 63
o
C with a 50/50 liquid mixture of A&B
(L
3
V
3
on the diagram), the vapor would
have a composition of 80% A & 20% B at
equilibrium.


Simple & Fractional Distillation
Column Efficiency - How pure can you get!!
A common measure of the efficiency of a Fractionation
Column is given by its number of Theoretical Plates
One Theoretical Plate is equivalent to a Simple
Distillation, i.e., one Vaporization / Condensation Cycle
The smaller the boiling point difference, the greater the
number of theoretical plates a fractionating column
must have to achieve separation of mixtures

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Boiling Point Number of
Difference Theoretical Plates

108 1
54 3
20 10
7 30
4 50
2 100
Simple & Fractional Distillation
Distillation Equipment Setup
Note: Equipment used in distillation experiment is expensive
Use care to avoid breakage
ASK BEFORE YOU ACT!!
Equipment
Heating Block (or sand bath) & Heating Plate
50 mL round bottom Distilling Flask (with boiling chip)
Distillation Head
Thermometer & Thermometer Adapter
Vigreux Fractionation Column (second group only)
Aluminum foil for Vigreux Column & Distillation Head
Water Jacket Condenser (with rubber tubing for water)
Receiving containers 2 10 mL graduated cylinders &
6 labeled vials with sealing caps
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Simple & Fractional Distillation
Distillation Equipment Setup (Cont)
Use 2 ring stands to support apparatus.
Attach clamp to Ring Stand & the Condenser
Attach clamp to other Ring Stand & Distillation
Head
Use Blue Plastic Clamp to secure Water Jacket
Condenser to neck of Distillation Head
Use Blue Plastic Clamp to secure Distillation Head (or
Vigreaux Column) to Distillation Flask
Insert thermometer through adapter so that the bulb
is positioned inch below opening to the Condenser
NOTE: Wrap the Distillation Head, Vigreux Column, and
Distillation Flask in Aluminum foil to improve heat
insulation
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Simple & Fractional Distillation
Typical Distillation Setup

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Simple & Fractional Distillation
Elements of The Experiment
Two Distillations
Simple Distillation
Fractional Distillation with Vigreux Column
Work in groups of 4 (2 groups of 2 each)
First group - Simple Distillation
Second group - Fractional Distillation
Each group of 4 will share data, but reports will be
written independently
Each report must contain all of the raw data from the
group, i.e., from both distillations
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Simple & Fractional Distillation
Elements of The Experiment (Cont)
Simple and Fractional distillations
Note: Can be setup as a single (1) procedure
Note: In Procedure Description make note of addition of
the Vigreux column used in the Fractional Distillation
Construct Barchart of incremental volumes (y-axes) vs
temperature ranges (x-axes)
For both Simple Distillation & Fractional Distillation:
Determine Total volume recovered
Compute Percent volume recovered
Total Volume in temperature ranges
0 95
o
C; 95 105
o
C; 105 130
o
C
Compute % volume recovered in each fraction
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Simple & Fractional Distillation
Combine the volumes from the 1
st
& 2
nd
fractions and
refer to it as Fraction A
Assume the combined 1
st
& 2
nd
fractions (fraction A) is
Ethyl Acetate and the 3
rd
fraction (fraction B) is Butyl
Acetate
Determine the mass of each compound in fraction A and
in fraction B from their respective volumes and density
Compute the Moles of each compound in fraction A and
fraction B
Determine the total moles in each fraction
Compute mole fraction
Compute mole %

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Simple & Fractional Distillation
Data Collection
Place 20 mL of mixture in a 50 mL round bottom flask
Set Hot Plate setting to about 5
Use 10 mL graduated cylinder to collect distillate
Collect distillate in 5 degree increments recording the
incremental volume collected in the 5 degree interval
Note: 1
st
increment is from 0
o
C 65
o
C
Continue to collect incremental volumes in 5 degree
increments, until temperature reaches 95
o
C
Transfer the total volume collected in the graduated
cylinder up to 95
o
C to the first labeled vial
Continue to collect distillate in 5 degree increments
from 95
o
C to 105
o
C
Transfer the total volume collected between
95
o
C - 105
o
C into the second labeled vial
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Simple & Fractional Distillation
Data Collection (Cont)
Increase temperature setting of Hot Plate
Continue to collect 5 degree volume increments in the
graduated cylinder until 1 mL remains in the flask
Note: DO NOT DISTILL TO DRYNESS
Turn off heat
Allow liquid in Distillation Head & Vigreux column to
cool and drain into the Distillation Flask (Pot Residue)
Transfer the Pot Residue to the graduated cylinder
Determine the volume of Pot Residue
Transfer the contents of the graduated cylinder to the
third labeled vial
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Simple & Fractional Distillation
Data Collection (Cont)
Suggested Table Template For Distillation Data

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Simple Fractional
Temp Range Volume (mL) Volume (mL)
0-65
o
C
65-70
o
C
70-75
o
C
75-80
o
C
80-85
o
C
85-90
o
C
90-95
o
C
95-100
o
C
100-105
o
C
105-110
o
C
110-115
o
C
115-120
o
C
120-125
o
C
125-130
o
C
Pot Residue
Initial
Volume
Total Volume
Recovered
Incremental Volumes
For each 5
o
C temperature interval, record
the volume of distillate collected in that
temperature range.
Cumulative Volumes for the 0 95
o
C, 95
105
o
C, and the 105 - 130
o
C fractions, can
be computed by summing the incremental
volumes for each fraction.
Pot Residue
Pot Residue is the volume of undistilled
sample remaining in the Distillation Flask
after the Hot Plate is turned off.
Allow the apparatus to cool down; then
transfer the remaining liquid in the
Distillation Flask to the Graduated
Cylinder.
The Pot Residue becomes part of the final
increment of Distillate.
Vial #1
Vial #2
Vial #3
Simple & Fractional Distillation
Results
NOTE: The following data analysis scheme is to be applied
separately to both the Simple and Fractional data
First Vial - All the distillate up to 95
o
C
(Mainly Ethyl Acetate B.P. - 77.1
o
C)
Second Vial - All the distillate collected between
95-105
o
C
Third Vial - All distillate above 105
o
C
(Mainly Butyl Acetate B.P. 126.1
o
C)
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Simple & Fractional Distillation
Results (Cont)
1. Calculate the total volume of distillate recovered
2. Calculate the % Recovery of the distillate
(Total Final Volume / Initial Volume) x 100
3. Use Excel to plot a bar chart of temperature
increments on the x-axis and volume increments on
the y-axis
Note: First increment is 0 65
o
C
Draw perpendicular lines to the 95 & 110 degree
marks on the x-axis
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Simple & Fractional Distillation
Example BarChart
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28
1
st

Fraction
3
rd

Fraction
2
nd

Fraction
Simple & Fractional Distillation
Results (Cont)
4. Calculate the total volume to the left of the
95
o
C line (1
st
fraction)
Calculate the total volume in the zone between
95 & 105
o
C (2
nd
fraction)
Calculate the total volume to the right of the
105
o
C line (3
rd
fraction)
5. Calculate volume percent composition of each of the
three (3) fractions
Vol % 1
st
fraction = Vol 1
st
fraction / Total Vol
Rcvd x 100
Vol % 2
nd
fraction = Vol 2
nd
fraction / Total Vol
Rcvd x 100
Vol % 3
rd
fraction = Vol 3
rd
fraction / Total Vol
Rcvd x 100
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Simple & Fractional Distillation
6. Compute Masses of Ethyl & Butyl Acetate
Combine Fractions 1 & 2 and assume it is Ethyl
Acetate
Assume Fraction 3 is Butyl Acetate
Compute the Mass of Ethyl Acetate and Butyl
Acetate from the Volumes and Densities of the two
new fractions
7. Compute the Moles of compound in each fraction




8. Compute the Total Moles in the two fractions

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30
mole
grams
grams

Wgt Mol
Mass
Moles
Volume x Density Mass
Volume
Mass
Density


Simple & Fractional Distillation
Results (Cont)
9. Compute the Mole Fraction of each fraction
10. Compute the Mole % of each fraction

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31
100 x N % N Percentage Mole
100 x N % N Percentage Mole
1 N N
B Moles A Moles
B Moles
N Fraction Mole
B Moles A Moles
A Moles
N Fraction Mole
B B
A A
B A
B
A

Simple & Fractional Distillation

Example calculations
Mixture Example (1000 mL 60% / 40% by Volume)
Ethyl Acetate (600 mL) Den 0.895 g/mL
Mol Wgt 88.11 g/mole
Butyl Acetate (400 mL) Den 0.882 g/mL
Mol Wgt 116.16 g/mole
Compute moles from volume, density, molecular weight





Mole Fraction
Ethyl Acetate 6.095 / 9.132 = 0.667 x 100 = 66.7%
Butyl Acetate 3.037 / 9.132 = 0.333 x 100 = 33.3%

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600 mL0.895 g / mL
Ethyl Acetate = 6.095 moles
88.11 g / mole
400 mL0.882 g / mL
Butyl Acetate = 3.037 moles
116.16 g / mole
Total Moles = 9.132
Simple & Fractional Distillation
Mole Percent of Distillates by Gas Chromatography
Refer to Website notes on the Gas Chromatography of
Acetates Experiment
Refer to Gas Chromatogram of the Equimolar
Mixture
Use the TR
x
/Tr
i
thermal response correction factor
for the Ethyl Acetate & Butyl Acetate peaks to
adjust the distillate fraction peak areas
Obtain a Gas Chromatogram of the Standard Mixture
(A or B), whichever you used in the Simple &
Fractional Distillation experiment
Obtain Gas Chromatograms of each of the 3 vials
you collected from the Simple Distillation and each of
the 3 vials collected from the Fractional Distillation
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Simple & Fractional Distillation
Mole Percent of Distillates by Gas Chromatography (cont)
Compute the Peak Areas using Triangulation method
Note: There are two peaks on each Chromatogram
Adjust the peak areas for non-linear thermal response
NOTE: Use TR
s
/Tr
i
correction factor from the
equimolar mixture used in the GC Acetates experiment
Compute adjusted areas by multiplying measured areas
from distillate fraction chromatograms the by the
equimolar mixture TR
s
/Tr
i
correction factor
Compute total area for peaks on each chromatogram
Compute the Mole Fraction
Compute Mole Percent
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Simple & Fractional Distillation
Mole Percent by Refractive Index
Note: Add to Experiment only if directed by Instructor
Obtain temperature corrected Refractive Index values
for the Unknown mixture (A or B) and the 6 simple &
fractional distillation vials
Use MS Excel to create a standard regression curve
from the known Refractive Index (y-axis) and Mole
% Ethyl Acetate (x-axis) values in the table below
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Solutions of
Known Mole %
and Refractive
Index
Mole%
Ethyl
Acetate
Mole %
Butyl
Acetate
Measured
R.I.
Temperature
(
o
C)
Corrected
R.I.
Ref (20
o
C
100 0 1.3714 21.7 1.3722 1.3723
60 40 1.3813 21.7 1.3821
50 50 1.3839 21.7 1.3848
40 60 1.3856 21.7 1.3864
0 100 1.3932 21.7 1.3941 1.3941
Simple & Fractional Distillation
Mole % by Refractive Index (cont)
Open MS Excel
From previous slide enter Mole % Ethyl Acetate
values into column A of spread sheet
Enter Corrected Ref. Index values into column B
Select data in columns A & B
Select Format Cells from Task Bar
Select Number and 4 decimal places
Select Insert from Task Bar
Select Scatter Plot (2 clicks) to plot the data
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Simple & Fractional Distillation
Mole % by Refractive Index (cont)
Add a trend (regression) line and regression equation
to the plot
Click on a data point in the plot
Select Add a Trend Line
Select
Linear
Display Equation on Chart
Display R-Square value on Chart
Select and move Regression Equation to upper left
corner
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Simple & Fractional Distillation
Mole % by Refractive Index (cont)
Select Axis Titles
Select Horizontal Axis Title
Select Title Below Axis
Enter text - Mole % Ethyl Acetate
Select Chart Title
Select Above Chart
Enter text - Refractive Index(corr) vs. Mole
% Ethyl Acetate
Select and move chart labels as appropriate
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Simple & Fractional Distillation
Mole % by Refractive Index
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39
y = -0.0002x + 1.3949
R = 0.9913
1.3700
1.3750
1.3800
1.3850
1.3900
1.3950
1.4000
0 20 40 60 80 100 120
Corrected
Refractive
Index
Mole Percent Ethyl Acetate
Refractive Index (corr) vs. Mole Percent Ethyl Acetate
Simple & Fractional Distillation
Mole % Analysis by Refractive Index (cont)
The Mole % values of the unknown mixtures are
determined either:
Directly from the Regression Curve by selecting the
mole % value relative to its equivalent Refractive
Index value
Computed from the regression equation
Rearrange the equation as follows to compute
your Mole % values
y = - 0.00022 x + 1.3949
x (Mole %) = (1.3949 y (Measured R.I.) / 0.00022
Ex. Measured R.I. 1.3850
X = (1.3949 - 1.3850) / 0.00022
X = 45% Ethyl Acetate (55% Butyl Acetate)
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Report Preparation
The Report (Combined with GC Distillates Report)
Scan Chromatograms and insert files into report
Only one (1) procedure is required for the Distillation
Equipment setup, simple distillation, fractional
distillation. Use one table to report results
The Description for each procedure involving a
computation must include the computational logic
behind the equation used and the equation setup with
suitable definition of the variables
The Summary section restates the results in
paragraph form
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Report Preparation
The Report (Cont)
Each procedure that produces data includes both
Simple Distillation results and Fractional Distillation
results
For comparison purposes each Simple result should
be paired with its equivalent Fractional result
For example: The total volume recovered for the Simple
Distillation was 17.6 ml (88.0%), while the total volume
recovered from the Fractional Distillation was 18.3 mL
(91.5%)
Create separate procedures for the computation of
mass, moles, mole fraction, mole %
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Report Preparation
Analysis & Conclusion Section
Discuss the effectiveness of component separation
by Simple & Fractional Distillation based on:
Analysis of the bar chart of the incremental &
fractional volumes, including the significance of
the amounts in the 2
nd
fraction (95
o
C 105
o
C)
Mole % values from the computed mass (from
volume and density) of the fractional volumes
Mole % from peak areas obtained from Gas
Chromatography
Compare the results for the original undistilled
A or B mixture and the distillate fractions
Mole % from Refractive Index
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